Transfer process



Patented May 12, 1936 UNITED STATES PATENT O FFlCE' No Drawing.

11 Claims.

The present invention relates to improvements in transfer processes, and more particulary relates to transfer processes for effecting reproduction or transfer of designs, drawings, written and typewritten material and the like from an original or master copy.

In certain of the transfer or reproduction processes of the general character hereinbefore referred to, a master copy is prepared in -reverse by drawing, writing, typing or otherwise producing the design on a master sheet, behind which is a sheet of suitably prepared carbon paper with its inked surface facing the master sheet, so that color constituents of the ink on the carbon paper are transferred to the back of the sheet, forming a reverse copy of the design or writing. In preparing copies from this master sheet, the surface of the copy sheet is moistened with a liquid, usually a water-miscible alcoholic liquid, which has a solvent action on the dyes in the ink deposited on the master sheet from the carbon paper, and the moistened copy sheet is applied to the back of the master sheet, a positive image of the original-being thereby reproduced upon 2 the copy sheet. In'carrying out such processes hitherto, aqueous and alcoholic solvents have usually been employed in effecting the transfer and the dyes used in the carbon paperemployed have been water-soluble. Hence, the character of col- 30 ors available for use in such processess has been seriously limited inmany directions; for example, by lack of blacks and by lack of colors of greater fastness'to light; and the water-soluble character of the dyes has resulted in soiling the 35 fingers of users of the paper and insmudging and blurring impressions on handling.

In accordance with the present invention, the

coloring'matters, ordyes employed in the inks used in the transferprocess are of the character designated as oil-soluble, such as oil-soluble basic dyes and the organicacid salts of basic dyes, such dye substances being not appreciably watersoluble. In conjunction withsuch coloring matters, volatile non-aqueoussolvents are used in 45 effecting the transfer operation, such as oil-miscible solvents which are not water-soluble or miscible with water in any substantial proportions as well as alcohols, glycol ethers, and the like. 50 "Ihus, in carrying out the present invention, inthe preparation of the carbon papers carrying the coloring material or dye, I employ, for example, basic. azo and amino-azodyes such 'as azo-black, the azine dyes, such as the nigrosines, lndulines and the like, methyl violet, crystal violet,

' in certain cases hereinafter have been designated Incorporated, a corporation of West Virginia Application January 24, 1935, Serial No. 3,289

fuchsine, anthraquinone dyes and chrysoidine and the like with organic acids, such as the higher fatty acids, lactic acid, abietic acid, tannic acid, gallic acid, tartaric acid, chloro-acetic acids, chloro-benzoic acids, or the like, or mixtures 5 thereof. In general, I- prefer to employ such salts of the higher fatty acids, such as the stemates, oleates, palmitates, laurates,-abietates and the like as the sole or principal color constituents in the carbon paper coatings or transfer inks 10 used in practicing the present invention. In conjunction therewith, I employ in the transfer process non-aqueous transfer liquids orsolvents of a suitable volatility such as the lower alcohols, glycol others, the lower ketones, acetone, ethyl- 15 methyl ketone and the like, lower hydrocarbons,

' such as the narrow boiling-point range cleaners naphthas, volatile cholrinated hydrocarbons such as carbon tetrachloride, dichloroethane and the like and the fluorochloroethanes such as trifluor- 2o otrichloroethane, difluorotetrachloroethane and the like and various mixtures including such s0l-' vents. I have found particularly suitable the fiuorochloroethane products described in my copending application Serial No. '743,1 14, filed Sep- 25 tember 7, 1934.

By operating in accordance with the present invention, I have beenable to employ and secure colors of a character hitherto not available in such transfer processes, for example, fast colors and blacks or colors closely approximating blacks. To illustrate the invention, operations will be described wherein black or substantially black colors are employed, although as hereinafter more fully pointed out, dyes of the classification referred to above and effective for'the production of other colors may, of course, be employed.

Thus, in preparing thecolor mixture used in the carbon paper employed in the process, for securing blacks, I have found the organic acid 40 salts of the nigrosine and of the induline bases to be particularly suitable. When black copies are desired, themixtures prepared with nigrosine compounds give the blackest copies and'those prepared'with induline compounds give the most intense copies. While either the nigrosine or the induline compounds may be employed a1one,.I prefer to use mixtures thereof, suitably in proportion of one-fifth to one-half of the induline compound and four-fifths to one-half of the nigrosine compound, although these proportions m2", of course, be varied. Various commercial nigrosine and induline dyes differ slightly in their characteristics and physical properties, and

ill

for identification purposes by their commercial names and sources. Spirit-soluble nigrosine jet (General Dyestuif 'Co.) has been found to be advantageous as a color constituent, as it reduces the higher fatty acids, or mixtures thereof. In

general I prefer to employ the higher fatty acids, such as stearic, palmitic or oleic acid, and abietic acid, either alone or as the principal acid combined with the basic dye. I have found the use of stearic acid to be highly desirable, as the salts which it forms with the basic dyes are of high melting point and therefore the proportions of wax, higher alcohols or other hardening agents required in preparing the carbon paper may be reduced. The use therewith of varying proportions of other organic acids, such as lactic and tartaric acid, and particularly the latter is de-' sirable, as they reduce a tendency to tackiness or stickiness in the color coating. Thus, as the acid constituent of the dye, I may use mixtures of a fatty acid, such as stearic acid, with tartaric acid containing from one-tenth to one-third of the latter. These proportions may, of course, be varied according to the dye and the fatty acid employed.

In preparing the coating for the carbon paper used in the transfer process, in conjunction with the oil-soluble dye compound hardening agents miscible therewith are employed. For example, I may employ the harder waxes and wax-like bodies such as the halogenated naphthalenes, the

hard waxes of the character of carnauba wax,-

palm wax, japan wax, Montan wax and the like. Manufactured or synthetic substitutes for such waxes may. of-course, be employed, such as that known as I. G. wax S which is similar to Montan wax in itscharacteristics. It will be noted that the waxes preferably employed have melting point ranges from somewhat above 50 C. to somewhat below 100 C. It will be readily apparent that mixtures of these waxes may be employed to secure any desired characteristics.

Other modifying agents may be employed in the mixture; for example, higher alcohols such as cetyl or ceryl alcohol, stearol, oleoLpalmitol. lauryl alcohol, myrystyl alcohol, or the like, may be employed in suitable proportions for lessening stickiness and tackiness of the dye mixture applied to the carbon .paper used in the process. Mineral oil may be included in the mixture to modify the characteristics of the coating, preferably a refined or light'colored, viscous distillate oil of a viscosity of about 150-155 seconds Saybolt at F. The texture and smoothness of the mixture may also be improved and separation and granulation of waxes prevented by the addition of small proportions, in general less than 1% of fatty acid salts of alkyl and alcohol amines, such as of diethyl amine or triethanol amine stearate.

The proportions of the constituents of the mixture used on the carbon paper employed in the process may vary somewhat; for example, the proportion of dye base or mixture of dye bases may be from 0.5 to 2 parts; the acid constituent or fatty acid constituent or mixture thereof may and from one-half to one and one-halfparts of higher alcohols may be present. Minor proportions of insoluble pigments or fillers may be present, but are generally not desirable.

The following examples illustrate suitable mix-- 'tures containing oil-soluble basic dye compounds for use as a coating on carbon paper employed in carrying out the present invention.

In certain cases, available commercial products have been designated, in addition, by their trade names in some cases by their source or manufacturer.

Example No. 1

Parts Nigrosine base N (National Aniline Co.) 10 Stearic acid 10 Mixture of stearol, oleo and palmitol (Stenol) l0 carnauba wax 2 Example No. 2

- Parts Nigrosine base N 7 Induline base B 3 Stearic acid 7 Tartaric acid 3 Higher alcohols 10 Montan Wax or carnauba wax 2 Example No. 3

- Parts Nigrosine base N 10 Induline base B 8 Abietic. aci-d 3 Stearic acid 5 Cetyl alcohol 4 Carnauba wax 8 Mineral oil 12 These compositions may, of course, be widely modified as hereinbefore indicated, other suitable compositions being set forth in my copending application Serial No. 3,288,filed January 24, 1935. Other basic dyes may be employed in accordance with color desired.

The constituents of the'ink or coating may be melted together and thoroughly mixed and blended, thereby effecting combination of the basic dye with the organic acid constituents. The melted mixture may then be coated on carbon paper tissue in the usual manner, while molten, if desired. However, the induline and nigrosine dyes, upon being heated or subjected to high temperatures, particularly for appreciable lengths of time, may become thick, less soluble in solvents, and lose tinctorial strength. Hence in the preparation and application of these mixtures, they should be heated as little for as short periods as possible. A formula such as that of Example No. 4 supra. is particularly susceptible to heat, whereas a formula such as that of Example No.

3 is markedly less susceptible to heat. The abietic acid appears to reduce the sensitiveness of the induline and nigrosine bases (andsalts) to heat and the cetyl alcohol has a similar action.

In preparing carbon papers from color mixtures prepared in accordance with my invention, instead of applying the'mixture in molten form to the tissue, the mixture, prepared with a minimum ficie'nt solvent is incorporated, suitably by grinding or mixing at a temperature slightly below the boiling point of the solvent, to secure a paste which can be applied by the usual coating rolls. The weight of the solvent employed will vary somewhat and may be approximately equal to the weight of the color mixture. After thorough mixturethe mixture may be cooled to normal room temperatures and-applied at such temperatures.

The application of the coating mixture with a solvent of this manner results in a character of coating which gives results in the transfer process superior to those secured when the coating mixture is applied to the tissue in molten form. In the molten process the coating on the tissue has a glazed or impervious surface and In carrying out the transfer process in accordance with the present invention, a carbon ,paper having in its pigment layer coloring matters of the character hereinbefore described is applied to the back of the master sheet and the latter is then subjected to the customary operation of drawing, writing or typing to produce the desired design or written matter thereupon, the oil-soluble coloring matter on the carbon paper being transferred to the back of the master copy in the operation. A copy sheet is moistened with a suitable volatile, substantiallynon-aqueous solvent liquid. For this purpose lower alcohols containing up to about 5% water, lactones, volatile ethers of glycol or diethylene glycol or suitable mixtures containing them may be employed, as may also volatile hydrocarbons,

. halogenated hydrocarbons such as carbon tetrachloride, dichloroethane or preferably a fluorochloroethane or mixture of fluorochloroethanes such as is described in my prior application Serial No. 743,114hereinbefore referred to. Thus, the lower alcohols, such as methyl, ethyl, isopropyl or butyl alcohol may be employed, althoughethyl alcohol is preferred for its low'toxiclty, or naphthe, toluene or the like may be employed alone or in admixturewith other solvents. Thus, another suitable solvent mixture may contain from 60 to alcohol, from 5 to 10% acetone, from 3 to 8% ethyl ether of glycol and 10,to 25% of non-volatile solvent and oil-'misci a suitable volatile petroleum or solvent naph the. cut of a narrow range'of boiling points. Either the acetone or volatile glycol ether may be omitted from the solvent, the proportion of the remaining constituent being preferably in-' creased, these compounds aiding in blending or securing miscibility of the alcohol and hydrocarbon. Small amounts, say 1 to 4% of a relatively ble liquid, such may be included, as it aids in keeping the ink on the master copy in good condition for reuse:

as castor oil or butyl ether of diethylene glycol The copy sheet moistened with the selected solr As pointedout hereinbefore, by operating in accordance with the present invention it is possible to secure, in the copy sheets, colors having characteristics not hitherto reproducible, and

particularly colors that are fast and black .or substantially black colors. It is readily apparent that any desiredcolor may be secured by a suitable selection of the basic dye and of the organic acid used in connection therewith. Thus, as pointed out hereinbefore, the dye bases employed may also be such as methyl violet, crystal violet, fuchsine, the anthraquinone dyes, other azine, azo or amino-azo dyes, chrysoidine or the like. Furthermore, although in the description hereinbefore given, theoi1-soluble dyes or dye salts have been described in connection with their incorporation with the ink layers of carbon paper, it

is readily apparent that they may also be incorporated into pencils with wax or wax-like binders or into inks or typewriter ribbons for application tothe master copy.

Iclaim: 1. The process of reproduction which comprises applying to a master sheet an oil-soluble color substance to form a design in reverse, moistening a copy sheet with a volatile, substantially non-aqueous solvent and applying the moistened copy sheet to the side of the master sheet bearing said color substance, thereby transferring a portion of said color substance to said copy sheet to form the design thereon.

2. The process of reproduction which comprises applying to a master sheet an oil-soluble basic dye substance to form a design in reverse, moistening a copy sheet with a volatile substantially non-aqueous solvent and applying the mostened copy sheet to the side of the master sheet bearing said color substance, thereby transferring a portion of the color substance to said copy sheet to form the design thereon.

3. The process of reproduction which comprises applying to a master sheet an oilsoluble salt of a basic dye with an organic acid to form a,

design in reverse, moistening a copy sheet with a volatile substantially non-aqueous solvent and applying the moistened copy sheet to the side of the master sheet bearing said basic dye salt, thereby transferring a portion. of the dye substance to said copy sheet to form the design thereon.

4. The process of reproduction which comprises applying to a master sheet an oil-soluble salt of a basic dye with a fatty acid to form a design in reverse, moistening a copy sheet with a volatile, substantially non-aqueous solvent and applying the moistened copy sheet to the side of the master sheet bearing. said dye substance thereby transferring a portiomof the dye substance to said copy sheet to forma design thereon.

5. The process of reproduction which comprises applying to a master sheet an oil-soluble basic dye stearate to form a design in reverse,

with a volatile, cit-solvent halogenated hydro-i carbon and applying the moistened copy sheet to the side of the master sheet bearing said dye salt, thereby transferring a portion of the dye salt to said copy sheet toform the design thereon.

'7. The process of reproduction which comprises applying to a master sheet an oil-soluble salt of'a basic dye and an organic acid to form a design in reverse, moistening a. copy sheet with a volatile, oil-solvent fluorochloroethane and applying the inoistened copy sheet to the side of the master sheet bearing said dye salt, thereby transferring a portion of the dye salt to said copy sheet to form the design thereon. Y

8. The process of reproduction which comprises applying to a master sheet an oil-soluble color substance of the class consisting of nigrosine base and induline base fatty acid salts 'to form a design in reverse, moistening a copy sheet witha volatile flucrochloroethane and applying the moistened copy sheet to the side of the master sheet bearing said color substance, thereaccepts by transferring a portion of the color substance to said copy sheet to form a design thereon.

. 9. The process of effecting transfers which comprises applying to a master sheet a mixture of an oil-soluble basic dye substance and a hardening agent miscible therewith to form a design in reverse, moistening a copy sheet with a volatile, substantially non-aqueous solvent and applying the moistened copy sheet to the side of the master sheet bearing said color substance, thereby transferring a portion of the color substance to said copy sheet to form the design thereon.

- 10. The process of efiecting transfers which comprises applying to a master sheet a mixture of an oil-soluble salt of a basic dye with an organic acid and a hardening agent miscible therewithto form a design in reverse, moistening a copy sheet with a volatile, substantially nonaqueous solvent and applying the moistened copy sheet to the side of the master sheet bearing such ,color substance, thereby transferring a portion of the color substance to said copy sheet to form the design thereon. v t

11. The process of effecting transfers which comprises applying to a master sheet a mixture of an oil-soluble saltof a basic dye with an organic acid, a wax and a high molecular weight iattyalcohol to form a design in reverse, moistening a copy sheet with a volatile, substantially non-aqueous solvent and applyingthe moistened copy sheet to the side of the master sheet bearing the color substance, thereby transferring a portion of the color substance to said copy sheet to form the design thereof. 7

PAUL V. BROWER. 

